Patent GB-575260-A (GB)
Title: Improvements in or relating to the insolubilisation of hydroxylated polymers
IPC: C08B15/06
Filed: 1943-10-12
Abstract: The solubility or tendency to swell in water and other liquids of hydroxylated polymers such as cellulose, wood, cellulose derivatives, starch, or hydroxyl-containing synthetic resins, rubber derivatives, or synthetic rubber is reduced by causing the polymers to react with a monocyclic urea having on each cyclic urea nitrogen atom a methylol group etherified with an alcohol boiling at not more than 210 DEG  C. The reaction is effected at a temperature and for a time sufficient for the polymer to become insoluble in solvents for the untreated polymer.  The ring structure of the urea compound may be formed by the -NCN- atoms of urea and a radical Y which is a divalent acyclic organic radical of chain length 2 or 3, both terminal atoms being carbon, any other chain member being C, O, S, or tertiary nitrogen, and all the hydrogen atoms being attached only to carbon.  The radical Y may be -CH2OCH2-, -CH2SCH2-, <FORM:0575260/IV/1> , -CO-CO-, -CO-CH2-CO-, or -CO-CO-CO-.  The alcohols with which the methylol groups are etherified may be methyl, ethyl, propyl, butyl, octyl, benzyl, furfuryl, tetrahydrofurfuryl, methoxyethyl and ethoxyethyl alcohols.  The reaction with the polymer may be effected at 70-200 DEG  C. and the polymer may be in solid form or may be dissolved in a solvent. Yarns, fabrics, or films of the polymer may be impregnated with a solution of the urea compound and then heated after removal of the solvent.  The reaction may be effected in presence of a catalyst of the type used in acetal interchange reactions, e.g. an acidic catalyst, e.g. p-toluene-sulphonic acid, hydrochloric acid, p sulphuric acid, phosphoric acid, zinc chloride, ferric chloride, aluminium chloride, ammonium chloride, boron trifluoride, iodine and sulphonium iodides.  In the case of fibres and fabrics, the treatment improves the resiliency and crease-resistance.  The urea compound may be incorporated in moulding compositions, or coating compositions and the heat treatment to effect insolubilization of the polymer, e.g. cellulose nitrate, polyvinyl alcohol, partially hydrolysed polyvinyl acetate, alkyd resin with hydroxyl groups, hydroxylated nylon, hydroxylated urea-formaldehyde resin, hydroxylated neoprene, hydroxylated butadiene polymers, or hydroxylated rubber, may be effected after removal of any volatile solvent.  In an example, N,N1-bis-(methoxymethyl) uron with a little citric acid is dissolved in water.  Muslin is immersed in the solution, dried and heated, to obtain crease-resistance.  A solution of cellulose acetate in acetone containing N,N1-bis-(methoxymethyl) uron is cast to form a film which is aged and then heated until it becomes insoluble in acetone.  A solution of hydroxylated rubber in xylene containing N,N1-bis-(methoxymethyl) uron and p-toluene sulphonic acid is heated at 125-130 DEG  C.  The hydroxylated rubber becomes insoluble and the mass becomes stiff.  A solution of polyvinyl alcohol, water, N,N1-bis-(methoxymethyl) uron and a catalyst is cast to form a film. The dried film is rendered insoluble in water by heating to 80 DEG C.  Viscose rayon yarn is immersed in a solution of N,N1-bis-(methoxymethyl) uron in water.  It is removed and dried in cool air and then heated to 105 DEG  C.  The yarn is insoluble in cuprammonium solution; it shows reduced water absorption, and it has good elastic recovery from stretch. Viscose rayon is treated with tetrahydro - 1,3 - bis - (methoxymethyl) - 5 - methyl-2(1)-s-triazone.  A solution of polyvinyl alcohol in water containing N,N1-bis-(methoxymethyl) ethylene urea and a catalyst is cast to form a film.  The film is dried and then heated to render it insoluble in water.  A cellulose nitrate emulsion is prepared by mixing butyl alcohol, butyl acetate, methyl ethyl ketone, castor oil, cellulose nitrate, water, and N,N1-bis-(methoxymethyl) uron, and emulsifying this oily phase with a mixture of polyvinyl alcohol, water, petroleum naphtha, isopropyl naphthalene sulphonate, and aluminium chloride. The emulsion is used as an adhesive for joining cellulosic articles such as wooden blocks.  Other reagents which may be used for the hydroxylated polymer are: tetrahydro-1,3-bis-(methoxymethyl)-5-p-hydroxyethyl-2 (1)-s-triazone; 3,5-bis-(methoxymethyl) tetrahydro - 1,3,5 - thiadiazine - 4 - one; N,N1 - bis - (methoxymethyl) - parabanic acid; N,N1 - bis - (propoxymethyl) barbituric acid, and similar derivatives of hydantoin, hydro-uracil, isobarbituric acid and alloxan.ALSO:The solubility or tendency to swell in water and other liquids of hydroxylated polymers such as starch, or hydroxyl-containing synthetic resins, rubber derivatives, or synthetic rubber is reduced by causing the polymers to react with a monocyclic urea having on each cyclic urea nitrogen atom a methylol group etherified with an alcohol boiling at not more than 210 DEG  C.  The reaction is effected at a temperature and for a time sufficient for the polymer to become insoluble in solvents for the untreated polymer.  The ring structure of the urea compound may be formed by the -NCN- atoms of urea and a radical Y which is a divalent acyclic organic radical of chain length 2 or 3, both terminal atoms being carbon, any other chain member being C, O, S, or tertiary nitrogen, and all the hydrogen atoms being attached only to carbon.  The radical Y may be -CH2-OCH2-, -CH2-S-CH2-, <FORM:0575260/V/1> or -CO, -CO-CO-.  The alcohols with which the methylol groups are etherified may be methyl, ethyl, propyl, butyl, octyl, benzyl, furfuryl, tetrahydrofurfuryl, methoxyethyl and ethoxyethyl alcohols.  The reaction with the polymer may be effected at 70-200 DEG  C. and the polymer may be in solid form or may be dissolved in a solvent.  Yarns, fabrics, or films of the polymer may be impregnated with a solution of the urea compound and then heated after removal of the solvent.  The reaction may be effected in presence of a catalyst of the type used in acetal interchange reactions, e.g. an acidic catalyst, e.g. p-toluenesulphonic acid, hydrochloric acid, sulphuric acid, phosphoric acid, zinc chloride, p  ferric chloride, aluminium chloride, ammonium chloride, boron trifluoride, iodine and sulphonium iodides.  The urea compound may be incorporated in moulding compositions or coating compositions and the heat treatment to effect insolubilization of the polymer, e.g. hydroxylated neoprene, hydroxylated butadiene polymer or hydroxylated rubber may be effected after removal of any volatile solvent.  A solution of hydroxylated rubber in xylene containing N,N1 - bis - (methoxymethyl) uron and p-toluene sulphonic acid is heated at 125-130 DEG  C.  The hydroxylated rubber becomes insoluble and the mass becomes stiff. The hydroxylated rubber is obtained by heating a mixture of crepe rubber, 1,3,5-trioxane, zinc chloride and glacial acetic acid, then cooling, washing and blowing the rubbery mass with air, adding a little N-phenyl-alpha-naphthylamine and heating to complete the drying.  Other reagents which may be used for the hydroxylated polymer are: tetrahydro-1,3-bis-(methoxymethyl) - 5 - hydroxyethyl - 2(1) - s - triazone; 3,5-bis-(methoxymethyl) tetrahydro-1,3,5-thiadiazine-4-one; N,N1-bis-(methoxymethyl)-parabanic acid; N,N1-bis-(propoxymethyl) barbituric acid, and similar derivatives of hydrantoin, hydro-uracil, isobarbituric acid and alloxan.